US10968311B2 - Wholly aromatic liquid crystalline polyester resin, molded article, and electric and electronic components - Google Patents

Wholly aromatic liquid crystalline polyester resin, molded article, and electric and electronic components Download PDF

Info

Publication number
US10968311B2
US10968311B2 US16/498,664 US201816498664A US10968311B2 US 10968311 B2 US10968311 B2 US 10968311B2 US 201816498664 A US201816498664 A US 201816498664A US 10968311 B2 US10968311 B2 US 10968311B2
Authority
US
United States
Prior art keywords
mol
liquid crystalline
polyester resin
crystalline polyester
structural unit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US16/498,664
Other languages
English (en)
Other versions
US20200040133A1 (en
Inventor
Gosuke WASHINO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
JXTG Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JXTG Nippon Oil and Energy Corp filed Critical JXTG Nippon Oil and Energy Corp
Assigned to JXTG NIPPON OIL & ENERGY CORPORATION reassignment JXTG NIPPON OIL & ENERGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WASHINO, Gosuke
Publication of US20200040133A1 publication Critical patent/US20200040133A1/en
Assigned to ENEOS CORPORATION reassignment ENEOS CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: JXTG NIPPON OIL & ENERGY CORPORATION
Application granted granted Critical
Publication of US10968311B2 publication Critical patent/US10968311B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/191—Hydroquinones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0006—Dielectric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings

Definitions

  • the present invention relates to a wholly aromatic liquid crystalline polyester resin, in particular a wholly aromatic liquid crystalline polyester resin having an especially low dielectric tangent, a molded article comprising the wholly aromatic liquid crystalline polyester resin, and electric and electronic components comprising the molded article.
  • This transmission loss consists of conductor loss due to a conductor and dielectric loss due to a resin for insulation which constitutes the electric and electronic components such as substrates in the electronic and communication devices, and since the conductor loss is proportional to 0.5 power of the frequency used and the dielectric loss to 1 power of the frequency, the effect due to this dielectric loss becomes extremely large in the high frequency band, particularly in the GHz band.
  • the dielectric loss also increases in proportion to the dielectric tangent of the resin, a resin having a low dielectric tangent performance is required for preventing degradation of information.
  • Patent Document 1 proposes a liquid crystalline aromatic polyester comprising 2 or more of a structural unit derived from p- or m-hydroxybenzoic acid and a structural unit derived from hydroxynaphthoic acid as a liquid crystalline aromatic polyester which shows low dielectric tangent in the high frequency band.
  • the resin which constitutes the electric and electronic components is required to have a high heat resistance to the heat which occurs at the time of molding (film forming stability), and a molded article such as a film made by the use thereof has been required to have a high heat resistance to the heat treatment in which soldering and the like is used.
  • Patent Document 1 Japanese Laid-open Patent Application Publication No. 2004-250620
  • Patent Document 2 Japanese Laid-open Patent Application Publication No. 2002-179776
  • the present inventors have examined the performance of the wholly aromatic polyester resins with various compositions in the course of developing the wholly aromatic polyester resins well-balanced in heat resistance and processability while having a particularly low dielectric tangent.
  • the use of polyester resin as proposed in Patent Document 2 for example was found to have insufficient processability into a film or a fiber.
  • melt stretching property was found to be insufficient, which secures the processability and stretching processability when the resin is melted.
  • the present inventors intensively studied to find that a wholly aromatic liquid crystalline polyester resin having an excellent balance between the heat resistance and processability while having a notably low dielectric tangent is obtainable by adjusting the specific structural units to a specific composition ratio in the wholly aromatic liquid crystalline polyester resin.
  • the object of the present invention is to provide a wholly aromatic liquid crystalline polyester resin having an excellent balance between the heat resistance and processability while having a notably low dielectric tangent.
  • Another object of the present invention is to provide a molded article comprising the wholly aromatic liquid crystalline polyester resin and electric and electronic components comprising the molded article.
  • the wholly aromatic liquid crystalline polyester resin according to the present invention comprises,
  • composition ratio (mol %) of said structural units (I) to (IV) is characterized by satisfying the following conditions:
  • composition ratio (mol %) of the structural units (I) to (IV) satisfies the following conditions:
  • structural unit (III) is preferably represented by the following formula:
  • Ar 1 is selected from the group consisting of a phenyl group, a biphenyl group, a naphtyl group, an anthryl group, and a phenanthryl group, optionally having a substituent group.
  • structural unit (IV) is preferably represented by the following formula:
  • Ar 2 is selected from the group consisting of a phenyl group, a biphenyl group, a naphtyl group, an anthryl group, and a phenanthryl group, optionally having a substituent group.
  • the draw ratio of a melt strand extruded under the conditions in which the temperature is +20° C. the melting point of the liquid crystalline polyester resin and the shear rate is 1000 s ⁇ 1 is preferably 10 times or more.
  • the dielectric tangent of the wholly aromatic liquid crystalline polyester resin in measurement frequency of 10 GHz is preferably 0.85 ⁇ 10 ⁇ 3 or less.
  • the dielectric tangent of the wholly aromatic liquid crystalline polyester resin in measurement frequency of 82 GHz is preferably less than 3.5 ⁇ 10 ⁇ 3 .
  • the dielectric tangents at 30° C. and 100° C. of the wholly aromatic liquid crystalline polyester resin in measurement frequency of 34 GHz are less than 2.0 ⁇ 10 ⁇ 3 and less than 4.0 ⁇ 10 ⁇ 3 respectively.
  • the change rate of the dielectric tangent from 30° C. to 100° C. of the wholly aromatic liquid crystalline polyester resin in measurement frequency 34 GHz is preferably less than 3.0 ⁇ 10 ⁇ 5 /° C.
  • the melting point of the wholly aromatic liquid crystalline polyester resin is preferably 290° C. or more.
  • the melt viscosity at a temperature of +20° C. the melting point of the liquid crystalline polyester resin and the shear rate of 1000 s ⁇ 1 is preferably from 20 to 150 Pa ⁇ s.
  • the molded article according to the present invention is characterized in that it comprises the above-described wholly aromatic liquid crystalline polyester resin.
  • the molded article is preferably in the form of a film.
  • the molded article is preferably in the form of a fibre.
  • the molded article is preferably an injection molded article.
  • the electric and electronic components according to the present invention are characterized in that the above-described molded article is comprised.
  • the present invention it is possible to attain a wholly aromatic liquid crystalline polyester resin having well-balanced properties of heat resistance and processability while having a notably low dielectric tangent by selecting specific structural units as the units forming the wholly aromatic liquid crystalline polyester resin and also by selecting a specific composition ratio thereof. That is to say, the use of a wholly aromatic liquid crystalline polyester resin according to the present invention will improve the heat resistance against heat treatment of the prepared molded article as well as film forming property and spinning stability. Therefore, it is possible to prevent the quality degradation of the emission signals in electric and electronic devices or telecommunication devices which use signals of high frequency when the molded articles are processed and molded and used as products. Also, the wholly aromatic polyester resin of the present invention also has a high spinning property and film forming stability, as well as being suitable for injection molding, and the molded article made by use thereof have high stability against heat treatment in which soldering and the like is used.
  • FIG. 1 shows the measurement results of the dielectric tangent in various GHz frequency of the wholly aromatic polyester resin.
  • FIG. 2 shows the measurement results of the dielectric tangent of the wholly aromatic polyester resin in 34 GHz (temperature dependency from 30° C. to 100° C.).
  • the wholly aromatic liquid crystalline polyester resin according to the present invention comprises structural unit (I) derived from p-hydroxybenzoic acid, structural unit (II) derived from 6-hydroxy-2-naphthoic acid, structural unit (III) derived from an aromatic diol compound, and structural unit (IV) derived from an aromatic dicarboxylic acid, wherein the composition ratio (mol %) of said structural units (I) to (IV) in the wholly aromatic liquid crystalline polyester resin satisfies the following conditions:
  • composition ratio of structural unit (III) in the wholly aromatic liquid crystalline polyester resin is substantially equivalent to the composition ratio of structural unit (IV) (structural unit (III) # structural unit (IV)).
  • the lower limit of the total structural units from (I) to (IV) is preferably 90 mol % or more, more preferably 95 mol % or more, and further preferably 99 mol % or more, and the upper limit is preferably 100 mol % or less, based on the structural units of the entire wholly aromatic liquid crystalline polyester resin.
  • the wholly aromatic liquid crystalline polyester resin having such constitution an adequate melt stretching property will allow to impart stable processability into a fiber or a film. Also, it is possible to attain a wholly aromatic liquid crystalline polyester resin having a notably low dielectric tangent. Further, since the wholly aromatic liquid crystalline polyester resin can have a high melting point, it is possible to attain high heat resistance of the molded article prepared from the same against heat treatment.
  • the melt stretching property of the liquid crystalline polyester resin of the present invention can be evaluated by measuring the draw ratio of the melt strand.
  • the melting point of the liquid crystalline polyester resin and the shear rate is 1000 s ⁇ 1 , is preferably 10 times or more and more preferably 15 times or more.
  • the melt stretching property of the wholly aromatic liquid crystalline polyester resin can be measured by using CAPILOGRAPH 1D manufactured by Toyo Seiki Seisaku-sho, Ltd.
  • the dielectric tangent (measurement frequency: 10 GHz) of the wholly aromatic liquid crystalline polyester resin according to the present invention is preferably 0.85 ⁇ 10 ⁇ 3 or less, more preferably 0.80 ⁇ 10 ⁇ 3 or less, and further preferably 0.75 ⁇ 10 ⁇ 3 or less.
  • the dielectric tangent (measurement frequency: 82 GHz) of the wholly aromatic liquid crystalline polyester resin according to the present invention is preferably less than 3.5 ⁇ 10 ⁇ 3 , more preferably less than 3.0 ⁇ 10 ⁇ 3 , and further preferably less than 2.5 ⁇ 10 ⁇ 3 .
  • the wholly aromatic liquid crystalline polyester resin according to the present invention preferably has dielectric tangents at 30° C. and 100° C. (measurement frequency: 34 GHz) of less than 2.0 ⁇ 10 ⁇ 3 and less than 4.0 ⁇ 10 ⁇ 3 respectively, more preferably of less than 1.5 ⁇ 10 ⁇ 3 and less than 3.0 ⁇ 10 ⁇ 3 respectively, and further preferably of less than 1.0 ⁇ 10 ⁇ 3 and less than 2.0 ⁇ 10 ⁇ 3 respectively.
  • the change rate of the dielectric tangent from 30° C. to 100° C. in measurement frequency of 34 GHz is preferably less than 3.0 ⁇ 10 ⁇ 5 /° C., more preferably less than 2.2 ⁇ 10 ⁇ 5 /° C., and further preferably less than 1.5 ⁇ 10 ⁇ 5 /° C.
  • the dielectric tangent of the wholly aromatic liquid crystalline polyester resin in 10 GHz can be measured by split post dielectric resonator method (SPDR method) by means of Network Analyzer N5247A from Keysight Technologies. Measurements in other frequencies of the dielectric tangent can be carried out by means of cylindrical cavity resonator method.
  • SPDR method split post dielectric resonator method
  • the value of the dielectric tangent is, unless otherwise specified, the value measured at 23° C., under ambient atmosphere, and humidity of 60%.
  • the lower limit of the melting point of the wholly aromatic liquid crystalline polyester resin according to the present invention is preferably 290° C. or more, more preferably 295° C. or more, further preferably 300° C. or more, and further more preferably 310° C. or more, and the upper limit is preferably 350° C. or less, more preferably 345° C. or less, and further preferably 340° C. or less.
  • the melting point of the wholly aromatic liquid crystalline polyester resin is in accordance with the test method of ISO11357, ASTM D3418 and can be measured by, for example, the differential scanning calorimeter (DSC) manufactured by Hitachi High-Tech Science Corporation.
  • DSC differential scanning calorimeter
  • melt viscosity of the liquid crystalline polyester resin according to the present invention has a lower limit of preferably 20 Pa ⁇ s or more and more preferably 30 Pa ⁇ s or more, and an upper limit of preferably 150 Pa ⁇ s or less, more preferably 125 Pa ⁇ s or less, and further preferably 100 Pa ⁇ s or less, under the temperature of +20° C. the melting point of the liquid crystalline polyester resin and the shear rate of 1000 s ⁇ 1 .
  • the melt viscosity of the wholly aromatic liquid crystalline polyester resin is in accordance with JIS K7199 and can be measured by using CAPILOGRAPH 1D manufactured by Toyo Seiki Seisaku-sho., Ltd.
  • Liquid crystallinity of the wholly aromatic liquid crystalline polyester resin according to the present invention can be confirmed by means of a polarizing microscope manufactured by Olympus Corporation (product name: BH-2) with a microscope heating stage manufactured by Mettler (product name: FP82HT), observing the presence/absence of optical anisotropy after heat melting the wholly aromatic liquid crystalline polyester resin on the microscope heating stage.
  • the wholly aromatic liquid crystalline polyester resin comprises structural unit (I) derived from p-hydroxybenzoic acid which is expressed by formula (I) described below, and the composition ratio (mol %) of structural unit (I) in the wholly aromatic liquid crystalline polyester resin is 2 mol % to 9 mol %.
  • the upper limit of the composition ratio (mol %) of structural unit (I) is preferably 8 mol % or less, more preferably 7 mol % or less, and further preferably 6 mol % or less.
  • Monomers which give structural unit (I) include p-hydroxybenzoic acid (HBA, formula (1) as below), the acetylated product, ester derivative, acid halide thereof, and the like.
  • the wholly aromatic liquid crystalline polyester resin comprises structural unit (II) derived from 6-hydroxy-2-naphthoic acid which is expressed by formula (II) described below, and the composition ratio (mol %) of structural unit (II) in the wholly aromatic liquid crystalline polyester resin is 40 mol % to 75 mol %.
  • the lower limit of the composition ratio (mol %) of structural unit (II) is preferably 48 mol % or more, more preferably 50 mol % or more, further preferably 55 mol % or more, and further more preferably 57 mol % or more, and the upper limit is preferably 72 mol % or less, more preferably 70 mol % or less, and further preferably 65 mol % or less.
  • Monomers which give structural unit (II) include 6-hydroxy-2-naphthoic acid (HNA, formula (2) as described below), the acetylated product, ester derivative, acid halide thereof, and the like.
  • HNA 6-hydroxy-2-naphthoic acid
  • the wholly aromatic liquid crystalline polyester resin comprises structural unit (III) derived from an aromatic diol compound, and the composition ratio (mol %) of structural unit (III) in the liquid crystalline polyester is 9 mol % to 24 mol %.
  • the lower limit of the composition ratio (mol %) of structural unit (III) is preferably 10 mol % or more, more preferably 12 mol % or more, and further preferably 14 mol % or more, and the upper limit is preferably 23 mol % or less, and more preferably 22 mol % or less.
  • structural unit (III) is represented by the following formula (III).
  • Ar 1 in the above-described formula is selected from the group consisting of a phenyl group, a biphenyl group, a naphtyl group, an anthryl group, and a phenanthryl group, optionally having a substituent group.
  • the phenyl group and the biphenyl group are more preferable.
  • the substituent group includes hydrogen, an alkyl group, an alkoxy group, and fluorine and the like. Number of carbons which the alkyl group has is preferably from 1 to 10 and more preferably from 1 to 5.
  • the alkyl group may be straight chained or branched.
  • the alkoxy group has 1 to 10 carbons and more preferably 1 to 5 carbons.
  • Monomers which give structural unit (III) include for example, 4,4-dihydroxybiphenyl (BP, formula (3) as below), hydroquinone (HQ, formula (4) as below), methylhydroquinone (MeHQ, formula (5) as below), and the acylated products thereof.
  • the wholly aromatic liquid crystalline polyester resin comprises structural unit (IV) derived from an aromatic dicarboxylic acid, and the composition ratio (mol %) of structural unit (IV) in the liquid crystalline polyester is 9 mol % to 24 mol %.
  • the lower limit of the composition ratio (mol %) of structural unit (IV) is preferably 10 mol % or more, more preferably 12 mol % or more, and further preferably 14 mol % or more, and the upper limit is preferably 23 mol % or less, and more preferably 22 mol % or less.
  • structural unit (IV) is represented by the following formula (IV).
  • Ar 2 in the above-described formula is selected from the group consisting of a phenyl group, a biphenyl group, a naphtyl group, an anthryl group, and a phenanthryl group, optionally having a substituent group.
  • the phenyl group is more preferable.
  • the substituent group includes hydrogen, an alkyl group, an alkoxy group, and fluorine and the like. Number of carbons which the alkyl group has is preferably from 1 to 10 and more preferably from 1 to 5.
  • the alkyl group may be straight chained or branched.
  • the alkoxy group has 1 to 10 carbons and more preferably 1 to 5 carbons.
  • Monomers which give structural unit (IV) include for example, terephthalic acid (TPA, formula (6) as below), isophthalic acid (IPA, formula (7) as below), 2,6-naphtalene dicarboxylic acid (NADA, formula (8) as below), and ester derivatives, acid halides thereof and the like.
  • the monomer which gives structural unit (IV) is preferably a single monomer, and when 2 or more of the monomers are combined, the proportion of the main monomer is preferably 65% or more, more preferably 70% or more, and further preferably 80 mol % or more.
  • the wholly aromatic liquid crystalline polyester resin according to the present invention can be prepared by polymerization of the monomers giving structural units (I) to (IV) with conventionally known methods such as melt polymerization, solid state polymerization, solution polymerization, and slurry polymerization.
  • the wholly aromatic liquid crystalline polyester resin according to the present invention can only be prepared by melt polymerization. Preparation is also possible by a two-stage polymerization in which melt polymerization is carried out which gives a prepolymer which is further subjected to solid state polymerization.
  • the melt polymerization is preferably carried out in the presence of 1.05 to 1.15 mol equivalent of acetic anhydride based on the total hydroxyl groups which the monomers have and under acetic acid reflux, the monomers giving the above-described structural units (I) to (IV) being incorporated in prescribed combination to make 100 mol %.
  • the prepolymer obtained by melt polymerization is cooled and solidified, subsequently triturated into a powder form or a flake form, and then preferably, a known solid state polymerization method is taken, the example of the method involving thermal treatment of the prepolymer resin for 1 to 30 hours at a temperature range from 200 to 350° C. under an inert atmosphere such as nitrogen or under vacuum.
  • the solid state polymerization may be carried out while stirring or in a static state without stirring.
  • the polymerization reaction may be carried out with or without the use of a catalyst.
  • the catalyst used can be those conventionally known as a catalyst for polymerization of polyester, including metal salt catalysts such as magnesium acetate, tin (I) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, and organic compound catalysts such as nitrogen containing heterocyclic compounds such as N-methyl imidazole.
  • the amount of catalysts used is preferably, without particular limitation, 0.0001 to 0.1 parts by weight based on the total amount of 100 parts by weight of the monomers.
  • the polymerization reactor used in the melt polymerization is preferably, without particular limitation, a reactor used for reaction of a general highly viscous fluid.
  • reactors include types of anchor, multi-stage, spiral band, spiral shaft, and the like, or stirred tank polymerization reactors equipped with a stirrer having stirring blades in various shapes formed by modifying such types, or mixing devices which are generally used for kneading resins such as a kneader, a roll mill, a bunbury mixer, and the like.
  • a molded article according to the present invention comprises the wholly aromatic liquid crystalline polyester resin, and the shape thereof is appropriately changed depending on the application, examples being, without particular limitation, in the form of a film, a plate, a fiber, and the like.
  • the molded article according to the present invention may comprise other resins than the wholly aromatic liquid crystalline polyester resin, as long as the effect of the present invention is not compromised.
  • polyester resins such as polyethylene terephthalate, polyethylene naphtalate, polyarylate, and polybutyrene terephthalate
  • polyolefin resins such as polyethylene and polypropylene
  • vinyl resins such as cycloolefin polymer and polyvinylchloride
  • (meth) acryl resins such as polyacrylate, polymethacrylate, and polymethyl methacrylate
  • polyphenylene ether resin polyacetal resin
  • polyamide resin imide resins
  • imide resins such as polyimide and polyether imide
  • polystyrene resins such as polystyrene, high-impact polystyrene
  • AS resin and ABS resin thermosetting resin such as epoxy resin, cellulose resin, polyether ether ketone resin, fluorine resin and polycarbonate resin
  • the molded article according to the present invention may comprise other additives, for example, a colorant, a dispersing agent, a plasticizer, an antioxidant, a curing agent, a flame retardant, a heat stabilizer, a UV absorber, an antistat, and a surfactant, as long as the effect of the present invention is not compromised.
  • a colorant for example, a colorant, a dispersing agent, a plasticizer, an antioxidant, a curing agent, a flame retardant, a heat stabilizer, a UV absorber, an antistat, and a surfactant, as long as the effect of the present invention is not compromised.
  • the molded article according to the present invention can be obtained by subjecting a mixture comprising the wholly aromatic liquid crystalline polyester resin and optionally other resins or additives to press molding, foam molding, injection molding, extrusion molding, and punch molding.
  • the mixture can be obtained by melt kneading the wholly aromatic liquid crystalline polyester resin, etc., by using a banbury mixer, a kneader, a single or twin screw extruder, and the like.
  • the molded article is preferably in a film form.
  • the film can be obtained by a conventionally known method, for example, extrusion molding such as inflation molding and melt extrusion molding, and solution casting method.
  • the film thus obtained may be a single layered film consisted of the wholly aromatic liquid crystalline polyester resin, or may be a multi-layered film with different kinds of materials.
  • the molded films by melt extrusion or solution casting may be subjected to stretching process in a single or twin screw, for the purpose of improving the dimension stability and mechanical properties. Thermal treatment may be carried out for the purpose of removing anisotropy or improving the heat resistance of the film.
  • the molded article is preferably in a fiber form.
  • Fibers can be obtained by conventionally known methods such as by melt spinning method, solution spinning method, and the like.
  • the fibers may be made solely of the wholly aromatic liquid crystalline polyester resin, or may be mixed with other resins.
  • Electric and electronic components according to the present invention comprise the above-described molded article, examples of which being an antenna, a high-speed transmission connector, a CPU socket, a circuit board, a flexible printed circuit board (FPC), a circuit board for lamination, a millimeter wave or a quasi-millimeter radar such as a radar for collision prevention, RFID tag, a condenser, an inverter part, an insulation film, a coating material for a cable, an insulation material of a secondary battery such as a lithium-ion battery, a vibrating plate of a speaker used in electronic devices and telecommunication devices such as ETC, GPS, wireless LAN and a mobile phone, and the like.
  • the electric and electronic components comprise a molded article (e.g., an injection molded article or a film, etc.) which comprises the wholly aromatic liquid crystalline polyester resin.
  • HBA p-hydroxybenzoic acid
  • HNA 6-hydroxy-2-naphthoic acid
  • BP 4,4-dihydroxybiphenyl
  • TPA terephthalic acid
  • the polymerization vessel made into a state where acetic acid was distilled out was subjected to temperature elevation at 0.5° C./min, and the polymerization product was taken out when the temperature of the melt product in the vessel reached 300° C., and cooled to solidify.
  • the obtained polymerization product was triturated into the size which will pass through a sieve having a sieve opening of 2.0 mm to obtain a prepolymer.
  • the prepolymer obtained as above was subjected to temperature elevation from room temperature to 300° C. over 14 hours by using a heating machine with an oven manufactured by Yamato Scientific Co., Ltd, and subsequently, the temperature was kept at 300° C. for 2 hours to carry out solid state polymerization. Subsequently, heat was naturally released at room temperature to obtain a wholly aromatic liquid crystalline polyester resin.
  • the wholly aromatic liquid crystalline polyester resin specimen was heat melted on a microscope heating stage by using a polarization microscope manufactured by Olympus Corporation (product name: BH-2) with a hot stage for microscopes manufactured by Mettler (product name: FP82HT) to confirm liquid crystallinity by the presence/absence of optical anisotropy.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 3 mol %, HNA 54 mol %, BP 21.5 mol %, and TPA 21.5 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 6 mol %, HNA 54 mol %, BP 20 mol %, and TPA 20 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 3 mol %, HNA 55 mol %, BP 21 mol %, and TPA 21 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 55 mol %, BP 20 mol %, and TPA 20 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 8 mol %, HNA 55 mol %, BP 18.5 mol %, and TPA 18.5 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 57 mol %, BP 19 mol %, and TPA 19 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 2 mol %, HNA 60 mol %, BP 19 mol %, and TPA 19 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 3 mol %, HNA 60 mol %, BP 18.5 mol %, and TPA 18.5 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 60 mol %, BP 17.5 mol %, and TPA 17.5 mol %, and the retention time at 300° C. was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 8 mol %, HNA 60 mol %, BP 16 mol %, and TPA 16 mol %, the final temperature of solid state polymerization was changed to 295° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 2 mol %, HNA 65 mol %, BP 16.5 mol %, and TPA 16.5 mol %, and the retention time at 300° C. was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 2 mol %, HNA 65 mol %, BP 14.5 mol %, methyl hydroquinone (MeHQ) 2 mol %, and TPA 16.5 mol %, the final temperature of solid state polymerization was changed to 295° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • MeHQ methyl hydroquinone
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 65 mol %, BP 15 mol %, and TPA 15 mol %, and the retention time at 300° C. was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 65 mol %, BP 15 mol %, TPA 13 mol %, and 2,6-naphtalene dicarboxylic acid (NADA) 2 mol %, the final temperature of solid state polymerization was changed to 295° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • NADA 2,6-naphtalene dicarboxylic acid
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 65 mol %, BP 15 mol %, TPA 14 mol %, and NADA 1 mol %, the final temperature of solid state polymerization was changed to 295° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 65 mol %, BP 15 mol %, TPA 10 mol %, and NADA 5 mol %, the final temperature of solid state polymerization was changed to 295° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 8 mol %, HNA 65 mol %, BP 13.5 mol %, and TPA 13.5 mol %, the final temperature of solid state polymerization was changed to 295° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 3 mol %, HNA 68 mol %, BP 14.5 mol %, and TPA 14.5 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 6 mol %, HNA 68 mol %, BP 13 mol %, and TPA 13 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 5 mol %, HNA 70 mol %, BP 12.5 mol %, and TPA 12.5 mol %, and the retention time at 300° C. was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 9 mol %, HNA 72 mol %, BP 9.5 mol %, and TPA 9.5 mol %, the final temperature of solid state polymerization was changed to 280° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 6 mol %, HNA 40 mol %, BP 27 mol %, and TPA 27 mol %, and the final temperature of solid state polymerization was changed to 305° C., and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 2 mol %, HNA 48 mol %, BP 25 mol %, and TPA 25 mol %, and the final temperature of solid state polymerization was changed to 310° C., and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 1 mol %, HNA 54 mol %, BP 22.5 mol %, and TPA 22.5 mol %, and the final temperature of solid state polymerization was changed to 310° C., and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 1 mol %, HNA 60 mol %, BP 19.5 mol %, and TPA 19.5 mol %, and the final temperature of solid state polymerization was changed to 305° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 10 mol %, HNA 65 mol %, BP 12.5 mol %, and TPA 12.5 mol %, and the final temperature of solid state polymerization was changed to 290° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 10 mol %, HNA 70 mol %, BP 10 mol %, and TPA 10 mol %, and the final temperature of solid state polymerization was changed to 290° C., and the retention time was changed to 1 hour, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 8 mol %, HNA 75 mol %, BP 8.5 mol %, and TPA 8.5 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HNA 60 mol %, BP 20 mol %, TPA 15 mol %, and isophtalic acid (IPA) 5 mol %, and then liquid crystalline property was confirmed in a similar manner as above.
  • Liquid crystalline polyester resin was obtained in a similar manner as Example 1, except that the monomer feed was changed to HBA 73 mol % and HNA 27 mol % and the final temperature of solid state polymerization was changed to 270° C., and then liquid crystalline property was confirmed in a similar manner as above.
  • the withdrawing rate the end point of measurement was obtained from the point where the withdrawing rate reached the measuring limit of the device of 200 m/min or the point where the strand broke, upon elevating the withdrawing rate at a rate of 400 m/min from the initial rate of 40 m/min.
  • melt strand could not be appropriately set up on the series of pulley and the wind-up roller due to lack of the melt stretching property, melt viscosity, or melt tension, or which measurement was not possible because the melt stretching property was below the measuring limit of the device were indicated as “ ⁇ ”.
  • the wholly aromatic liquid crystalline polyester resins obtained from the Examples and Comparative Examples were heat melted and injection molded at a condition in which the temperature was from the melting point to +30° C. the melting point to make flat plate test specimens of 30 mm ⁇ 30 mm ⁇ 0.4 mm.
  • dielectric tangent of frequency of 10 GHz was measured by a split post dielectric resonator method (SPDR method), using Network Analyzer N5247A from Keysight Technologies. The measured results are summarized in Table 1.
  • SPDR method split post dielectric resonator method
  • the wholly aromatic liquid crystalline polyester resins obtained from Example 8 and Comparative Examples 8 and 9 were heat melted and injection molded at a condition in which the temperature was from the melting point to +30° C. the melting point to make flat plate samples of 30 mm ⁇ 30 mm ⁇ 0.4 mm. Subsequently, square flat plates in 13 mm square were cut from the center of these flat plate samples to make test specimens. These test specimens were loaded on to a resonator for 100 GHz at graduate School of Engineering, Utsunomiya University, Kogami Lab. & Shimizu Lab., and by cylindrical cavity resonator method, the dielectric tangent of frequency of 82 GHz was measured at room temperature.
  • the wholly aromatic liquid crystalline polyester resins obtained from Example 8 and Comparative Examples 8 and 9 were heat melted and injection molded at a condition in which the temperature was from the melting point to melting point+30° C. to make flat plate samples of 30 mm ⁇ 30 mm ⁇ 0.4 mm. Subsequently, square flat plates in 13 mm square were cut from the center of these flat plate samples to make test specimens. These test specimens were loaded on to a resonator for 36 GHz at graduate School of Engineering Utsunomiya University, Kogami Lab. & Shimizu Lab., and by cylindrical cavity resonator method, the dielectric tangent of frequency of 34 GHz was measured while changing the measuring temperature.
  • the detailed measuring method is as follows.
  • the resonator to which the specimen was set was placed in a constant-temperature tank, and after setting the set-up temperature of the constant-temperature tank to 105° C., the tank was left to stand for 2 hours. Thereafter, the constant-temperature tank was set to 20° C. and the inner temperature of the tank was left to naturally fall, and the dielectric tangent was measured this time at every 1° C. The results are shown in FIG. 2 . Further, the dielectric tangent at 30° C. and 100° C. and the change rate of dielectric tangent from 30° C. to 100° C. are shown in Table 3.
  • the melting points of the wholly aromatic liquid crystalline polyester resins obtained in the Examples and Comparative Examples were measured by a differential scanning calorimeter (DSC) manufactured by Hitachi High-Tech Science Corporation.
  • DSC differential scanning calorimeter
  • the melting point (Tm 2 ) was determined from an endotherm peak which was obtained when the temperature was elevated from room temperature to 360-380° C. at a temperature increasing rate of 10° C./min to melt the polymer completely, and subsequently lowered to 30° C. at a rate of 10° C./min, and further elevated to 380° C. at a rate of 10° C./min.
  • the peak of the endotherm peak of the first round (Tm 1 ) was determined as the melting point (t).
  • Table 1 The measured results are summarized in Table 1.
  • the melt viscosity (Pa ⁇ s) at a temperature of +20° C. the melting point in a shear rate of 1000 s ⁇ 1 of the wholly aromatic liquid crystalline polyester resins obtained from the Examples and Comparative Examples were measured in accordance with JIS K7199 by using a capillary rheometer viscometer (CAPILOGRAPH 1D manufactured by Toyo Seiki Seisaku-sho., Ltd.) and capillary with inner diameter of 1 mm. The measured results are summarized in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
US16/498,664 2017-03-28 2018-03-28 Wholly aromatic liquid crystalline polyester resin, molded article, and electric and electronic components Active US10968311B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JPJP2017-063735 2017-03-28
JP2017-063735 2017-03-28
JP2017063735 2017-03-28
PCT/JP2018/012868 WO2018181525A1 (ja) 2017-03-28 2018-03-28 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品

Publications (2)

Publication Number Publication Date
US20200040133A1 US20200040133A1 (en) 2020-02-06
US10968311B2 true US10968311B2 (en) 2021-04-06

Family

ID=63677815

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/498,664 Active US10968311B2 (en) 2017-03-28 2018-03-28 Wholly aromatic liquid crystalline polyester resin, molded article, and electric and electronic components

Country Status (7)

Country Link
US (1) US10968311B2 (zh)
EP (1) EP3604380A4 (zh)
JP (1) JP6530148B2 (zh)
KR (1) KR102213912B1 (zh)
CN (1) CN110494471B (zh)
TW (1) TWI735768B (zh)
WO (1) WO2018181525A1 (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11258184B2 (en) 2019-08-21 2022-02-22 Ticona Llc Antenna system including a polymer composition having a low dissipation factor
US11555113B2 (en) 2019-09-10 2023-01-17 Ticona Llc Liquid crystalline polymer composition
US11637365B2 (en) 2019-08-21 2023-04-25 Ticona Llc Polymer composition for use in an antenna system
US11646760B2 (en) 2019-09-23 2023-05-09 Ticona Llc RF filter for use at 5G frequencies
US11721888B2 (en) 2019-11-11 2023-08-08 Ticona Llc Antenna cover including a polymer composition having a low dielectric constant and dissipation factor
US11728559B2 (en) 2021-02-18 2023-08-15 Ticona Llc Polymer composition for use in an antenna system
US11729908B2 (en) 2020-02-26 2023-08-15 Ticona Llc Circuit structure
US11912817B2 (en) 2019-09-10 2024-02-27 Ticona Llc Polymer composition for laser direct structuring
US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7324752B2 (ja) * 2018-06-26 2023-08-10 Ｅｎｅｏｓ株式会社 熱処理により誘電正接を低減できる全芳香族液晶ポリエステル樹脂を含む樹脂成形品および電気電子部品
JP6852233B2 (ja) * 2019-04-03 2021-03-31 ポリプラスチックス株式会社 全芳香族ポリエステル及びポリエステル樹脂組成物
US20210075162A1 (en) * 2019-09-10 2021-03-11 Ticona Llc Electrical Connector Formed from a Polymer Composition having a Low Dielectric Constant and Dissipation Factor
JP7365861B2 (ja) * 2019-11-06 2023-10-20 上野製薬株式会社 フィルム用ポリエチレンテレフタレート樹脂組成物
EP4091817A4 (en) * 2020-01-17 2023-12-20 Toray Industries, Inc. LIQUID CRYSTAL POLYESTER RESIN, LIQUID CRYSTAL POLYESTER RESIN COMPOSITION, MOLDED PRODUCT, LAMINATED BODY AND LIQUID CRYSTAL POLYESTER RESIN FILM AND PRODUCTION METHOD THEREOF
WO2021161918A1 (ja) * 2020-02-14 2021-08-19 Ｅｎｅｏｓ株式会社 液晶ポリエステル、液晶ポリエステルの製造方法、樹脂溶液、金属張積層板、及び、金属張積層板の製造方法
JP2021147476A (ja) * 2020-03-18 2021-09-27 Ｅｎｅｏｓ株式会社 樹脂組成物および該樹脂組成物からなる樹脂成形品
JP7458924B2 (ja) 2020-07-21 2024-04-01 Ｅｎｅｏｓ株式会社 液晶ポリエステル樹脂、成形品、および電気電子部品
JP2022021174A (ja) * 2020-07-21 2022-02-02 Ｅｎｅｏｓ株式会社 液晶ポリエステル樹脂、成形品、および電気電子部品
CN112409582B (zh) * 2020-11-16 2022-12-02 金发科技股份有限公司 一种液晶聚合物树脂及其制备方法和应用
CN112646140A (zh) * 2020-12-09 2021-04-13 上海普利特化工新材料有限公司 一种适用于纤维制备且具备低介电损耗正切值的全芳香族液晶聚酯树脂及其应用
KR102524571B1 (ko) * 2020-12-29 2023-04-21 세양폴리머주식회사 저유전상수 및 저유전손실율을 지닌 유동성이 향상된 액정 폴리에스테르 조성물
CN114106307A (zh) * 2021-11-17 2022-03-01 浙江大学 一种支化热致芳香族液晶聚酯的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002179776A (ja) 2000-09-22 2002-06-26 Polyplastics Co 全芳香族ポリエステル及びポリエステル樹脂組成物
US20040044169A1 (en) 2000-09-22 2004-03-04 Toshiaki Yokota Wholly aromatic polyester and polyester resin composition
JP2004250620A (ja) 2003-02-21 2004-09-09 Sumitomo Chem Co Ltd 絶縁材料用液晶性芳香族ポリエステルおよびその樹脂組成物
JP2006001990A (ja) 2004-06-16 2006-01-05 Sumitomo Chemical Co Ltd 芳香族液晶ポリエステルフィルムおよび積層体
US20090111926A1 (en) 2007-10-30 2009-04-30 Ueno Fine Chemicals Industry, Ltd. Liquid-crystalline polyester blend
JP2015183159A (ja) * 2014-03-26 2015-10-22 上野製薬株式会社 液晶ポリエステルブレンド
JP2017179127A (ja) 2016-03-30 2017-10-05 Ｊｘｔｇエネルギー株式会社 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品
WO2018008612A1 (ja) * 2016-07-04 2018-01-11 Ｊｘｔｇエネルギー株式会社 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6833405B1 (en) * 1998-07-31 2004-12-21 E. I. Du Pont De Nemours And Company Compositions containing liquid crystalline polymers
JP5036106B2 (ja) * 2001-06-15 2012-09-26 上野製薬株式会社 サーモトロピック液晶ポリマー
JP5017060B2 (ja) * 2007-10-30 2012-09-05 上野製薬株式会社 全芳香族液晶ポリエステル
JP2009263640A (ja) * 2008-04-04 2009-11-12 Sumitomo Chemical Co Ltd 熱伝導性樹脂組成物及びその用途
CN101831306A (zh) * 2009-03-13 2010-09-15 上海普利特复合材料股份有限公司 一种热致性液晶高分子材料
US8580145B2 (en) * 2009-08-11 2013-11-12 Toray Industries, Inc. Liquid crystalline polyester and process for producing same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002179776A (ja) 2000-09-22 2002-06-26 Polyplastics Co 全芳香族ポリエステル及びポリエステル樹脂組成物
US20040044169A1 (en) 2000-09-22 2004-03-04 Toshiaki Yokota Wholly aromatic polyester and polyester resin composition
JP2004250620A (ja) 2003-02-21 2004-09-09 Sumitomo Chem Co Ltd 絶縁材料用液晶性芳香族ポリエステルおよびその樹脂組成物
JP2006001990A (ja) 2004-06-16 2006-01-05 Sumitomo Chemical Co Ltd 芳香族液晶ポリエステルフィルムおよび積層体
US20090111926A1 (en) 2007-10-30 2009-04-30 Ueno Fine Chemicals Industry, Ltd. Liquid-crystalline polyester blend
JP2009108191A (ja) 2007-10-30 2009-05-21 Ueno Fine Chem Ind Ltd 液晶ポリエステルブレンド
JP2015183159A (ja) * 2014-03-26 2015-10-22 上野製薬株式会社 液晶ポリエステルブレンド
JP2017179127A (ja) 2016-03-30 2017-10-05 Ｊｘｔｇエネルギー株式会社 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品
WO2018008612A1 (ja) * 2016-07-04 2018-01-11 Ｊｘｔｇエネルギー株式会社 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Extended European Search Report dated Oct. 27, 2020 in corresponding European Application No. 18775501.2.
International Preliminary Report on Patentability dated Oct. 10, 2019 in International Application No. PCT/JP2018/012868.
International Search Report dated Jun. 5, 2018 in International Application No. PCT/JP2018/012868.
JP-2015183159-A abstract, Kihara Masahiro (Year: 2015). *
WO 2018008612 abstract, Washino Gosuke (Year: 2018). *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11258184B2 (en) 2019-08-21 2022-02-22 Ticona Llc Antenna system including a polymer composition having a low dissipation factor
US11637365B2 (en) 2019-08-21 2023-04-25 Ticona Llc Polymer composition for use in an antenna system
US11705641B2 (en) 2019-08-21 2023-07-18 Ticoan Llc Antenna system including a polymer composition having a low dissipation factor
US11555113B2 (en) 2019-09-10 2023-01-17 Ticona Llc Liquid crystalline polymer composition
US11912817B2 (en) 2019-09-10 2024-02-27 Ticona Llc Polymer composition for laser direct structuring
US11646760B2 (en) 2019-09-23 2023-05-09 Ticona Llc RF filter for use at 5G frequencies
US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies
US11721888B2 (en) 2019-11-11 2023-08-08 Ticona Llc Antenna cover including a polymer composition having a low dielectric constant and dissipation factor
US11729908B2 (en) 2020-02-26 2023-08-15 Ticona Llc Circuit structure
US11728559B2 (en) 2021-02-18 2023-08-15 Ticona Llc Polymer composition for use in an antenna system

Also Published As

Publication number Publication date
EP3604380A4 (en) 2020-11-25
JP6530148B2 (ja) 2019-06-12
KR102213912B1 (ko) 2021-02-05
US20200040133A1 (en) 2020-02-06
TWI735768B (zh) 2021-08-11
KR20190127766A (ko) 2019-11-13
JPWO2018181525A1 (ja) 2019-06-27
CN110494471B (zh) 2021-11-02
WO2018181525A1 (ja) 2018-10-04
EP3604380A1 (en) 2020-02-05
TW201840639A (zh) 2018-11-16
CN110494471A (zh) 2019-11-22

Similar Documents

Publication Publication Date Title
US10968311B2 (en) Wholly aromatic liquid crystalline polyester resin, molded article, and electric and electronic components
US10822453B2 (en) Wholly aromatic liquid crystalline polyester resin, molded article, and electric and electronic components
US11505647B2 (en) Resin molded article comprising wholly aromatic liquid crystalline polyester resin capable of reducing dielectric loss tangent by heat treatment and electrical and electronic component
JP6900151B2 (ja) 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品
US20220073732A1 (en) Resin composition and resin molded article comprising the same
JP7458924B2 (ja) 液晶ポリエステル樹脂、成形品、および電気電子部品
CN115916866A (zh) 液晶聚酯树脂、成型品和电气电子零件
US20230257519A1 (en) Liquid crystal polyester resin, molded article, and electrical/electronic component

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

AS Assignment

Owner name: JXTG NIPPON OIL & ENERGY CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WASHINO, GOSUKE;REEL/FRAME:051160/0389

Effective date: 20191106

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

AS Assignment

Owner name: ENEOS CORPORATION, JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:JXTG NIPPON OIL & ENERGY CORPORATION;REEL/FRAME:055526/0276

Effective date: 20200703

STCF Information on status: patent grant

Free format text: PATENTED CASE